CN107381501B - Application of cerium and compound in improving hydrogen storage performance of amide-hydride system - Google Patents

Application of cerium and compound in improving hydrogen storage performance of amide-hydride system Download PDF

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CN107381501B
CN107381501B CN201710613093.9A CN201710613093A CN107381501B CN 107381501 B CN107381501 B CN 107381501B CN 201710613093 A CN201710613093 A CN 201710613093A CN 107381501 B CN107381501 B CN 107381501B
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metal
cerium
compound
hydride
cef
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CN107381501A (en
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林怀俊
张鹏
张治国
李卫
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Jinan University
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Jinan University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Abstract

The invention discloses a metal cerium and application of a cerium compound in improving the hydrogen storage performance of a metal-based amide-hydride composite system, wherein the cerium compound comprises CeO2、CeF3And CeF4. Use ofWhen in use, metal cerium and/or cerium compound is doped into the metal-based amide-hydride composite system by a mechanical ball milling method, and the addition amount is 1-10 wt%. The metal cerium and the cerium compound can completely inhibit the ammonia decomposition of the metal-based amide-hydride complex system in the hydrogen desorption process, obviously reduce the hydrogen desorption temperature and improve the hydrogen desorption rate; and after a plurality of hydrogen absorption and desorption cycles, the metal cerium and the cerium compound still have excellent catalytic effect on the metal-based amide-hydride composite system.

Description

Application of cerium and compound in improving hydrogen storage performance of amide-hydride system
Technical Field
The invention belongs to the field of hydrogen storage materials and catalytic modification thereof, and particularly relates to application of metal cerium and cerium compounds in improving the hydrogen storage performance of a metal-based amide-hydride composite system.
Background
Metal-based amide-hydride composite systems, e.g. LiNH2LiH and Mg (NH)2)2The-2 LiH system is one of the most potential high-capacity hydrogen storage materials developed in recent years, and has more appropriate hydrogen absorption and desorption thermodynamic properties, higher reversible hydrogen storage capacity and better hydrogen absorption and desorption cycle stability. However, the metal-based amide-hydride composite system has too large hydrogen absorption and desorption activation energy, so that the hydrogen absorption and desorption dynamic performance is too slow, the hydrogen absorption and desorption operation temperature needs to reach about 200 ℃, ammonia gas is released in the hydrogen desorption process, and the cycle performance is poor, so that the metal-based amide-hydride composite system is not suitable for being used as a hydrogen source of a vehicle-mounted fuel cell.
The reduction of kinetic barrier of hydrogen absorption and desorption reaction by doping the catalyst is an effective way for improving the hydrogen storage performance of the metal-based amide-hydride composite system. Studies show that TiCl3Can remarkably improve Mg (NH)2)2Dehydrogenation performance of the 2LiH system, but TiCl3The catalytic effect of (a) disappears after undergoing two hydrogen absorption and desorption cycles. Further, KH, KOH, single-walled carbon nanotubes, V, V2O5、VCl3、TiN、TaN、NaH、Li3N、LaH3And Li3AlH6The compounds can improve the hydrogen absorption and desorption kinetic properties of the metal-based amide-hydride composite system to a certain extent, but the improvement effect is still very limited, and a small amount of ammonia gas is still released in the dehydrogenation process of the metal-based amide-hydride composite system.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the application of the metal cerium and the cerium compound in improving the hydrogen storage performance of a metal-based amide-hydride composite system.
The purpose of the invention is realized by the following technical scheme:
the application of metal cerium and cerium compound in improving the hydrogen storage performance of a metal-based amide-hydride composite system;
the cerium compound comprises CeO2、CeF3And CeF4；
The metal-based amide-hydride composite system is preferably LiNH2LiH or Mg (NH)2)2-2LiH；
When in use, the metal cerium and/or cerium compound is doped into the metal-based amide-hydride composite system by a mechanical ball milling method; the addition amount of the metal cerium and/or the cerium compound is 1-10 wt% (calculated by the mass sum of the metal cerium and/or the cerium compound and the metal-based amide-hydride composite system);
preferably, under the protection of inert gas, metal cerium and/or cerium compound, metal-based amide and metal-based hydride are mixed uniformly and ball-milled;
the preferred ball milling time is 1-20h, the ball-material ratio is (30-100):1, and the revolution speed of the ball mill is 300-.
Compared with the prior art, the invention has the following advantages and effects:
the metal cerium and the cerium compound are used for improving the hydrogen storage performance of the metal-based amide-hydride composite system, the doping process is simple, and the doped metal-based amide-hydride composite system has the characteristics of hydrogen discharge working temperature, high hydrogen discharge rate and the like suitable for FC (fiber channel) work.
1-10 wt% of metal cerium and cerium compound are doped, so that ammonia decomposition of the metal-based amide-hydride complex system in the hydrogen desorption process can be completely inhibited, the hydrogen desorption temperature is obviously reduced, and the hydrogen desorption rate is improved; and after a plurality of hydrogen absorption and desorption cycles, the metal cerium and the cerium compound still have excellent catalytic effect on the metal-based amide-hydride composite system.
Drawings
FIG. 1 is LiNH2LiH composite and LiNH doped with cerium metal and cerium compound2-XRD pattern of LiH complex; wherein, a-LiNH2LiH composite, b-doped 10 wt.% Ce, c-doped 10 wt.% CeO2D-doping 10 wt.% of CeF3E-doping 10 wt.% of CeF4。
FIG. 2 is LiNH2LiH composite and LiNH doped with cerium metal and cerium compound2-thermogravimetric-gas-phase mass-spectral curves of LiH complexes.
FIG. 3 is LiNH2LiH composite and LiNH doped with cerium metal and cerium compound2Isothermal dehydrogenation curves of LiH complexes at different temperatures.
FIG. 4 is LiNH2LiH complexes and doped CeF4LiNH of (A)2-gas mass spectrum profile of LiH complex.
FIG. 5 is a CeF-doped semiconductor device4LiNH of (A)2-thermogravimetric-gas-phase mass spectrometry curve of LiH complex after two cycles.
FIG. 6 is Mg (NH)2)2-2LiH complex and doped CeF4Mg (NH) of2)2-gas mass spectrum profile of 2LiH complex.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
LiNH was added in a molar ratio of 1:1 in a glove box filled with argon gas2Mixing with LiH, and adding 10 wt% (based on metal cerium and/or cerium compound and metal amino)Mass sum of compound-hydride composite system as calculation reference) of Ce, CeO2，CeF3And CeF4Fully mixing, putting into a ball milling tank with a switch valve, pre-vacuumizing the ball milling tank, and ball milling and mixing on a planetary wheel type ball mill with a ball-material ratio of 60:1, a rotation speed of 400rpm and ball milling time of 2 hours.
LiNH2The purity is 95 percent; the purity of LiH is 99.9%; ce, CeO2，CeF3And CeF4The purity was 99%.
FIG. 1 shows a cerium-doped cerium oxide doped with CeO2、CeF3Or CeF4LiNH of (A)2X-ray diffraction curves of LiH samples, indicating LiNH2LiH and the cerium metals and cerium compounds are all mechanically mixed and no reaction occurs between the two during ball milling.
The hydrogen absorption and desorption performance of the test sample is as follows: and taking out and weighing the ball-milled sample in a glove box filled with argon, and performing thermogravimetric-gas mass spectrometry. As can be seen from FIG. 2, LiNH2Doping of the LiH sample with Ce, CeO2，CeF3Or CeF4The dehydrogenation temperature is reduced, and the ammonia decomposition phenomenon is not generated in the dehydrogenation process.
FIG. 3 is a LiNH after ball milling2LiH composite (without addition of cerium compound) and doped with Ce, CeO respectively2、CeF3Or CeF4LiNH of (A)2Isothermal dehydrogenation kinetic curves of LiH complex at different temperatures, indicating that the addition of cerium metal and cerium compound significantly increases LiNH2Dehydrogenation kinetics of LiH composite LiNH with addition of cerium metal and cerium compound2The isothermal dehydrogenation rate of the-LiH complex at 180 ℃, 200 ℃ and 220 ℃ was increased by about 3 times.
Example 2
LiNH was added in a molar ratio of 1:1 in a glove box filled with argon gas2Mixing with LiH, and adding 1 wt%, 3 wt% or 10 wt% (based on the mass sum of the metal cerium and/or cerium compound and the metal amide-hydride composite system) CeF4Mixing, placing into ball milling tank with switch valve, pre-pumpingAfter vacuum, ball milling and mixing are carried out on a planetary wheel type ball mill, the ball-material ratio is 50:1, the rotating speed is 400rpm, and the ball milling time is 4 hours.
LiNH2The purity is 95 percent; the purity of LiH is 99.9%; CeF4The purity was 99%.
The hydrogen absorption and desorption performance of the test sample is as follows: and taking out and weighing the ball-milled sample in a glove box filled with argon, and performing thermogravimetric-gas mass spectrometry. As can be seen from FIG. 4, LiNH2LiH samples doped with 1 wt%, 3 wt% or 10 wt% CeF4And then ammonia decomposition phenomenon is not generated in the dehydrogenation process.
Example 3
LiNH was added in a molar ratio of 1:1 in a glove box filled with argon gas2Mixing with LiH, adding 10 wt% (based on the mass sum of metal cerium and/or cerium compound and metal amide-hydride composite system) of CeF4Fully mixing, putting into a ball milling tank with a switch valve, pre-vacuumizing the ball milling tank, and ball milling and mixing on a planetary wheel type ball mill with a ball-material ratio of 80:1, a rotation speed of 400rpm and ball milling time of 5 hours. And (3) performing hydrogen absorption and desorption circulation on the ball-milled sample twice at 150 ℃ by using Sievert type gas-solid reaction testing equipment, wherein the hydrogen absorption pressure is 5MPa, the hydrogen absorption time is 4h, the dehydrogenation pressure is 0.01MPa, and the dehydrogenation time is 4 h.
LiNH2The purity is 95 percent; the purity of LiH is 99.9%; CeF4The purity was 99%.
Dehydrogenation performance of the test sample: and in a glove box filled with argon, taking out and weighing the sample after hydrogen absorption and desorption circulation, and performing thermogravimetric-gas mass spectrometry. As can be seen from FIG. 5, after 2 cycles of hydrogen absorption and desorption, LiNH was observed2LiH samples doped with 10 wt% CeF4The dehydrogenation process of (2) does not generate ammonia decomposition phenomenon.
Example 4
In a glove box filled with argon, Mg (NH) was added in a molar ratio of 1:22)2Mixing with LiH, and adding 1 wt%, 3 wt% or 10 wt% (based on the mass sum of the metal cerium and/or cerium compound and the metal amide-hydride composite system) CeF4Is sufficientMixing, putting into a ball milling tank with a switch valve, pre-vacuumizing the ball milling tank, and ball milling and mixing on a planetary wheel type ball mill with a ball-material ratio of 40:1, a rotation speed of 400rpm and ball milling time of 2 hours.
Mg(NH2)2The purity is 95 percent; the purity of LiH is 99.9%; CeF4The purity was 99%.
The hydrogen absorption and desorption performance of the test sample is as follows: and taking out and weighing the ball-milled sample in a glove box filled with argon, and performing thermogravimetric-gas mass spectrometry. As can be seen from FIG. 6, Mg (NH)2)2Samples of-2 LiH doped with 1 wt%, 3 wt% or 10 wt% CeF4And then ammonia decomposition phenomenon is not generated in the dehydrogenation process.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (2)

1. The application of metal cerium and cerium compound in improving the hydrogen storage performance of a metal-based amide-hydride composite system is characterized in that: the metal cerium and the cerium compound are used as catalysts;
the cerium compound comprises CeF3And CeF4；
The metal-based amide-hydride complex system is LiNH2LiH or Mg (NH)2)2-2LiH；
When in use, the metal cerium and/or cerium compound is doped into the metal-based amide-hydride composite system by a mechanical ball milling method; the addition amount of the metal cerium and/or the cerium compound is 1-10 wt%;
or, under the protection of inert gas, uniformly mixing and ball-milling the metal cerium and/or cerium compound, the metal-based amide and the metal-based hydride; the addition amount of the metal cerium and/or the cerium compound is 1-10 wt%.
2. The use of cerium metal and cerium compound as claimed in claim 1 for improving hydrogen storage performance of metal-based amide-hydride composite system, wherein: the ball milling time is 1-20h, the ball material ratio is (30-100):1, and the revolution speed of the ball mill is 300-500 rpm.
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JP2002320848A (en) * 2001-02-23 2002-11-05 Honda Motor Co Ltd Hydrogen storage material
US6967012B2 (en) * 2003-06-25 2005-11-22 General Motors Corporation Imide/amide hydrogen storage materials and methods
US7029649B2 (en) * 2003-08-26 2006-04-18 General Motors Corporation Combinations of hydrogen storage materials including amide/imide
US7601329B2 (en) * 2004-02-26 2009-10-13 Gm Global Technology Operations, Inc. Regeneration of hydrogen storage system materials and methods including hydrides and hydroxides
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